DE102009001382A1 - New polymer, obtained by reacting a polymer (containing ethylene repeating units, and dioxane repeating units) with alkyl ketene dimers useful e.g. to prepare coating on substrate, and an intermediate layer-foil for laminated glass plate - Google Patents

Abstract

Polymer, obtained by reacting a polymer (containing ethylene repeating units (I)-(III), and dioxane repeating units (IV)) with at least one alkyl ketene dimer (V), is new. Polymer, obtained by reacting a polymer (containing ethylene repeating units of formulae (-[CH(R10)-CH(OH)] a-) (I), (-[CH(R10)-CH(OR1)] b-) (II) and (-[C(R5)(R4)-C(R3)(R2)] c-) (III), and dioxane repeating units of formula (IV)) with at least one alkyl ketene dimer of formula (V), is new. R2-R5 : COCH 3or COCH 2CH 2; R6, R7 : H or 1-8C alkyl; R8, R9 : 8-30C alkyl, 8-16C alkyl, 1-20C alkyl substituted phenyl, 1-20C alkyl substituted cycloalkyl or aralkyl; R10 : H or 1-4C alkyl; a : 10-99.9 mole%; b : 20-0.1 mole%; c : 0-25 mole%; and d : 0-70 mole%. An independent claim is included for a foil comprising the above polymer. [Image].

Description

The The present invention relates to the modification of polyvinyl alcohols, Polyvinyl acetals or their derivatives by reaction with alkylketene dimers to give more hydrophobic or internally plasticized polymers.

Technical area

polyvinyl alcohol as the hydrolysis product of polyvinyl acetate is in various degrees of hydrolysis for a long time as water-soluble, d. H. hydrophilic binder system known. For different applications, especially in the paper industry would be less water-soluble or even water-insoluble polyvinyl alcohols are advantageous, because they have the water resistance or water vapor impermeability surface jobs on paper would.

The Reaction of polyvinyl alcohols with aldehydes leads to Polyvinyl acetals used as binders in the printing ink and ceramics industry, and in plasticized form as an intermediate layer in laminated glass production Find use. Again, this would be for some Applications of hydrophobic derivatives of advantage; could continue in the manufacture of laminated glass, the plasticizer compatibility, or Plasticizer absorption can be improved.

State of the art

On the papermaking field is the conversion of cellulose fibers, with ketene, especially with alkylketene dimers (AKD) known. hereby an improved ink-sizing of the papers is achieved.

So describes US 5,439,010 the production of wrapping paper from cigarettes by using a mixture of polyvinyl alcohol, a wet strength agent such. B. Polyamidaminepichlorhydrinharz (PAAE) and AKD. This blend significantly improves the sizing effect of the polyvinyl alcohol, with attachment of the AKD and PAAE resin to the cellulosic wet strength fiber and the polyvinyl alcohol improving the paper stiffness. This publication does not mention a reaction between AKD and the polyvinyl alcohol. Furthermore, the described mixture is prepared at temperatures of about 60 ° C, in which a chemical reaction between AKD and polyvinyl alcohol does not take place in an aqueous medium.

WO 2005/095710 A1 and US 6,676,806 disclose the sizing of paper with AKD and subsequent addition of polyvinyl alcohol or polyvinyl acetals as polymeric binders. Since the actual sizing reaction between AKD and the cellulose fiber takes place, a reaction between AKD and polyvinyl alcohol can be ruled out.

The simultaneous use of AKD and polyvinyl alcohol in papermaking is over EP 0 610 895 A1 known. Here, a polyvinyl alcohol stabilized dispersion of AKD is used as sizing agent. EP 0 610 895 describes that the actual sizing reaction takes place between AKD and the cellulose fiber. Accordingly, no reaction takes place in the dispersion between the AKD and the dispersing aid polyvinyl alcohol, since otherwise the AKD would no longer be available as a reactant for the cellulose. The dispersion is a physical mixture of the components.

In DE 43 23 560 the sizing of paper with a mixture of an amine-functionalized polyvinyl alcohol and AKD is described. Also, this publication does not mention a reaction between AKD and the polyvinyl alcohol. The reactive glue is based on the cellulose-reactive AKD additive, ie the AKD reacts with the cellulose and not with the polyvinyl alcohol. The functions of the amine-modified polyvinyl alcohol is unclear, but should be based on its basic action against the anionic cellulose or the added cationic starch.

task

task The present invention was therefore hydrophobically modified Polyvinyl alcohols and / or polyvinyl acetals and / or derivatives thereof To provide an improved hydrophobic Behavior or internal plasticization through newly introduced Have side chains.

Surprisingly has been found that said polymeric compounds in a simple manner with the readily available on an industrial scale AKD connections can be implemented and become products improved in terms of hydrophobicity and internal plasticization Properties lead.

The reaction of polyvinyl alcohols with unsubstituted diketene is out CH 300340 . CH 310838 as well as through H. Staudinger and M. Haeberle in Macromolecular Chem. 9.52 (1952) known. The reactions described here in glacial acetic acid take place at relatively low temperatures due to the unsubstituted nature of the diketene, resulting in polyvinylacetylacetates. The latter are not the subject of the present invention.

Presentation of the invention

• (a) in 10 bis 99,9 Mol%, bevorzugt 50 bis 99,9 Mol mit R₁₀ = H, C₁ bis C₄-Alkylrest

• (b) in 20–0,1 Mol%, bevorzugt 10–0,1 Mol% mit R₂ bis R₅ = COCH₃, COCH₂CH₃ R₁₀ = H, C₁ bis C₉-Alkylrest

• (c) in 0 bis 25 Mol% mit R₂ bis R₅ = H bis C₁ bis C₈-Alkylreste

• (d) in 0 bis 70 Mol% mit R₆, R₇ = H, C₁ bis C₈-Alkylreste

mit einem oder mehreren Alkylketendimeren (AKD) der allgemeinen Formel e)

• e) mit R₈, R₉ jeweils gleich oder verschieden = C₈ bis C₃₀-Alkylreste, C₈ bis C₁₆-Alkylreste, C₁ bis C₂₀-Alkyl substituierte Phenylreste, C₁ bis C₂₀-Alkyl substituierte Cycloalkylreste, Aralkylreste.

Subject of the present invention are Therefore, the reaction products of polymers which have the following repeating units:

• (A) in 10 to 99.9 mol%, preferably 50 to 99.9 mol with R ₁₀ = H, C ₁ to C ₄ alkyl

• (b) in 20-0.1 mol%, preferably 10-0.1 mol%, with R ₂ to R ₅ = COCH ₃ , COCH ₂ CH ₃ R ₁₀ = H, C ₁ to C ₉ -alkyl radical

• (c) in 0 to 25 mol% with R ₂ to R ₅ = H to C ₁ to C ₈ alkyl radicals

• (d) in 0 to 70 mol% with R ₆ , R ₇ = H, C ₁ to C ₈ alkyl radicals

with one or more alkylketene dimers (AKD) of the general formula e)

• e) with R ₈ , R _{9 are} each identical or different = C ₈ to C ₃₀ alkyl, C ₈ to C ₁₆ alkyl, C ₁ to C ₂₀ alkyl substituted phenyl, C ₁ to C ₂₀ alkyl substituted cycloalkyl, aralkyl ,

According to the invention, polyvinyl alcohols having a degree of hydrolysis of from 80 to 99.9 mol%, in particular from 90 to 99.9 mol%, and / or those having the repeating units a) and b) where R ₁ = are preferred as polymer with the repeating units a) and b) COCH ₃ and R ₁₀ = H used. Such polymers are available under the trade name "Mowiol" from Kuraray Europe GmbH in various degrees of hydrolysis.

Polymers with repeating units a), b) and c) are known under the trade name "Exeval" of Kuraray Europe GmbH, and under the trade name "Eval" of EVAL Europe nv. These polymers preferably contain 1 to 15 mol% of the repeat units c) (where R ₂ to R ₅ = H), 1 to 10 mol% repeat units b) with R ₁ = COCH ₃ and an amount of the vinyl alcohol groups adding to 100 mol% a) ,

Likewise, polymers having the repeating units a) to d), preferably a), b) and d), ie partially acetalized polyvinyl alcohols, suitable starting materials for a reaction according to the invention with the AKD e). The acetalated polyvinyl alcohols used may in particular be those obtained from the reaction of polyvinyl alcohol with butyraldehyde (polyvinyl butyral, PVB). These usually have a degree of acetalization (repeat unit d) with R ₆ = H and R ₇ = butyl) of 60 to 90 mol%, preferably 70 to 85 mol%. Furthermore, the residual acetate content (repeat unit b) with R ₁ = COCH ₃ ) is between 1 and 10 mol%; the residual vinyl alcohol content (repeat unit a) with R ₁₀ = H) is generally from 10 to 30 mol%.

One Another object of the invention is a method for implementation a polymer having repeating units a), b,) c) and d) in the stated amounts and meanings with at least one alkylketene dimer (AKD) e) in the stated amounts and meanings in organic solvents or in the polymer melt. Preferably, the polymer and the Alkylketene derivative in weight ratios of 50 to 99.9: 50 to 0.1, preferably from 75 to 98:25 to 2 used.

The Reaction can be in kneaders, stirred tanks or preferably in Extruders are performed.

The Reaction of said polymers with one or more chemical different AKD is preferably carried out in the absence of water. Under The absence of water becomes a water content in the context of this invention the reaction mixture of less than 2% by weight, preferably less than 1% by weight. and in particular less than 0.1% by weight.

As a polymer melt is also considered a molten mixture of the polymer and one or more plasticizers, wherein in the case of pure polyvinyl alcohol polyhydric alcohols and their derivatives, such as. As ethylene glycol, diethylene glycol, triethylene glycol, glycerol, polyethylene glycol and corresponding diols and triols come into question. For polyvinyl acetals, plasticizers such. For example, polyvinylbutyraldihexyl adipate (DHA) diisononyl-1,2-cyclohexanedicarboxylic acid (DINCH) or triethylene glycol bis-octanoate (3G8), possibly together with other plasticizers, proven.

kind and amount of plasticizer used are not particular Meaning, it is only a thermoplastic processing of the mixture be made possible at the following temperatures.

The Reaction preferably takes place at temperatures above 100 ° C., in particular above 150 ° C and more preferably above 200 ° C, with temperatures above 250 ° C avoided to avoid thermal decomposition phenomena should be.

eingesetzt, wobei bevorzugte Verbindungen für R₈ und R₉ jeweils gleich oder unterschiedlich Alkylreste (C_nH_2n+1 mit n = 8–30, bevorzugt n = 12–20), Hexadecenylreste, Nonylphenylreste, Nonylcyclohexylreste oder Phenylethylreste aufweisen. Besonders bevorzugt ist die Variante, nach der R8 = R9 = Alkylrest in der oben beschriebenen Form bedeutet. AKD wird als Festprodukt von der Firma Hercules unter dem Namen Aquapel^® 364 vertrieben.As alkyl ketene dimer (AKD) are preferably compounds of general formula e)

used, wherein preferred compounds for R ₈ and R ₉ each have the same or different alkyl radicals (C _n H _{2n + 1} with n = 8-30, preferably n = 12-20), hexadecenyl, Nonylphenylreste, Nonylcyclohexylreste or phenylethyl radicals. Particularly preferred is the variant according to which R8 = R9 = alkyl radical in the above-described form. AKD is sold as a solid product by the company Hercules under the name Aquapel ^® 364.

Without to be bound by a theory, it is assumed that AKD e) with the hydroxyl groups (a) of the polymers used with formation the following repeating unit f).

Around the invention desired effect to achieve the hydrophobization or internal plasticization, be at least 0.1 to a maximum of 50 mol% of the hydroxyl groups a) a polymer having repeating units a) to d) with alkyl diketene e) implemented.

The Reaction products can be used to make coatings on substrates, as an additive for the production of paper, in particular oil and grease-proof paper as a binder in paints and corrosion inhibitors, as a binder for ceramic green films, ceramic powder and metal powder, as a binder for photographic films or photothermal materials or as a binder for Printing inks and for the production of interlayer films for composite glazing be used.

The mentioned reaction products of the polymers with the repeating units a) to d) with the AKD of formula e) are suitable in particular for Production of films, z. B. as an interlayer films for Laminated glazings. Subject of the present invention are therefore also films containing the reaction products of polymers with the repeat units a) to d) with the AKD of the formula e), each with the specified quantities and meanings.

These Slides can only be made from these reaction products or from Mixtures of the reaction products with suitable plasticizers or from Mixtures of the reaction products with polymers with the repeating units a) to d), in particular partially acetalized polyvinyl alcohols such as polyvinyl butyral or mixtures thereof with one or more plasticizers.

Prefers Contain the films 60 bis according to the invention 85% by weight of the o. G. polymeric materials (i.e., reaction products optionally in admixture with polymers of repeating units a) to d)) and 15 to 40 wt.% Of at least one plasticizer.

Become Mixtures of polymers used, these contain at least 10 wt.%, Preferably at least 25 wt.% Of the inventive Reaction products. Particular preference is given to the reaction with the AKD and as a further mixture component the (chemically) same Polymers of identical type and proportion of units a) to d) used.

Prefers the films have a plasticizer content of at most 40% by weight, particularly preferably of not more than 38% by weight and in particular of maximum 36% by weight, with a plasticizer content of 15% by weight for reasons the processability of the film should not be fallen below. Inventive films can be a or more plasticizers. In general, the inventive Foils at least 24% by weight of plasticizer.

Particularly suitable as plasticizers for the preparation of the polymer melts and / or as a mixture component of the films are compounds selected from the group consisting of di-2-ethylhexyl sebacate (DOS), di-2-ethylhexyl adipate (DOA), di-2-ethylhexyl phthalate (DOP), dihexyl adipate (DHA), dibutyl sebacate (DBS), di-2-butoxyethyl sebacate (DBES), triethylene glycol bis-2-ethylhexanoate (3G8), triethylene glycol col-bis-n-heptanoate (3G7), tetraethylene glycol bis-n-heptanoate (4G7), di-2-butoxyethyl adipate (DBEA), di-2-butoxyethoxyethyl adipate (DBEEA).

When Polmer with the repeating units a) to d) can in particular partially acetalized polyvinyl alcohol, more preferably one with one or more aldehydes having 1 to 6 carbon atoms acetalized Polyvinyl alcohol (units a) and b)) with a degree of hydrolysis of at least 97% are used.

Next the reaction products contain the inventive Foils preferably uncrosslinked polyvinyl butyral (PVB, units a), b) and d)) by acetalization of polyvinyl alcohol with butyraldehyde is won.

The use of crosslinked polyvinyl acetals, especially crosslinked polyvinyl butyral (PVB) is also possible. Suitable crosslinked polyvinyl acetals are, for. In EP 1527107 B1 and WO 2004/063231 A1 (thermal self-crosslinking of carboxyl-containing polyvinyl acetals), EP 1606325 A1 (crosslinked with polyaldehydes polyvinyl acetals) and WO 03/020776 A1 (Crosslinked with glyoxylic polyvinyl acetals) described. The disclosure of these patent applications is fully incorporated by reference.

When Polyvinyl alcohol for acetalization may be used in the context of present invention also terpolymers of hydrolyzed vinyl acetate / ethylene copolymers be used. These compounds are usually at least 97 mol.% Hydrolyzed and contain 1 to 10 wt.% Based on ethylene Units (eg type "Exceval" of Kuraray Europe GmbH). The acetalization of these copolymers can be with one or several aldehydes having 1 to 6 carbon atoms, preferably butyraldehyde respectively.

polyvinyl contain in addition to the acetal units still from vinyl acetate and vinyl alcohol resulting units. The inventively used Polyvinyl acetals preferably have a vinyl alcohol content of 25-12, in particular 25-18% by weight. A vinyl alcohol content of 12% by weight should not be undercut. The vinyl acetate content is preferably below 5 wt.%, Preferably below 3 wt.% And in particular less than 2% by weight of the vinyl alcohol content and the residual acetate content the degree of acetalization can be calculated.

invention Films can be used for the production of laminated glazing in the Automotive and architectural sectors and for the manufacture of photovoltaic modules, as facade component, roof surfaces, conservatory cover, Soundproof wall, balcony or parapet element or as Part of window surfaces are used.

The adhesion of such films to glass is usually by the addition of adhesion regulators such. B. the in WO 03/033583 A1 disclosed alkali and / or alkaline earth metal salts of organic acids. Lithium, magnesium, calcium and / or zinc salts of organic acids (eg acetates) have proven to be particularly suitable. In addition, polyvinyl acetals from the manufacturing process often alkali and / or alkaline earth metal salts of inorganic acids, such as. For example, sodium chloride.

The basic production, composition and processing of films based on polyvinyl acetals is z. In EP 185 863 B1 . EP 1 118 258 B1 WO 02/102591 A1 . EP 1 118 258 B1 . EP 1 235 683 B1 or EP 387 148 B1 described.

to Lamination of a laminated body z. B. from two glass panes and an intermediate film according to the invention may be familiar to those skilled in the process with and without previous production of a pre-bond can be used.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - US 5439010 [0005]
• WO 2005/095710 A1 [0006]
• - US 6676806 [0006]
• - EP 0610895 A1 [0007]
• - EP 0610895 [0007]
• - DE 4323560 [0008]
• - CH 300340 [0011]
• - CH 310838 [0011]
• EP 1527107 B1 [0034]
• WO 2004/063231 A1 [0034]
• EP 1606325 A1 [0034]
• WO 03/020776 A1 [0034]
• WO 03/033583 A1 [0038]
• EP 185863 B1 [0039]
• - EP 1118258 B1 [0039, 0039]
• WO 02/102591 A1 [0039]
• - EP 1235683 B1 [0039]
• - EP 387148 B1 [0039]

Cited non-patent literature

• - H. Staudinger and M. Haegerle in Macromolecular Chem. 9, 52 (1952) [0011]

Claims (10)

Polymer obtainable by the reaction of a polymer containing the repeating units

(A) in 10 to 99.9 mol% with R ₁₀ = H, C ₁ to C ₄ alkyl

(b) in 20-0.1 mol% with R ₂ to R ₅ = COCH ₃ , COCH ₂ CH ₃ R ₁₀ = H, C ₁ to C ₄ alkyl

(c) in 0 to 25 mol% with R ₂ to R ₅ = H, C ₁ to C ₈ alkyl radicals

(d) in 0 to 70 mol% with R ₆ , R ₇ = H, C ₁ to C ₈ -alkyl radicals with at least one alkylketene dimer (AKD) of the general formula e)

e) with R ₈ , R _{9 are} each identical or different = C ₈ to C ₃₀ alkyl, C ₈ to C ₁₆ alkyl, C ₁ to C ₂₀ alkyl substituted phenyl, C ₁ to C ₂₀ alkyl substituted cycloalkyl, aralkyl , Polymer according to claim 1, characterized in that that the reaction takes place in the absence of water. Polymer according to claim 1, characterized in that that the reaction takes place in organic solvents. Polymer according to one of claims 1 to 3, characterized characterized in that the reaction takes place in a polymer melt. Process for the reaction of one or more polymers with the repeating units

(a) in 0 to 99.9 mol% with R ₁₀ = H, C ₁ to C ₄ alkyl

(b) in 20-0.1 mol% with R ₂ to R ₅ = COCH ₃ , COCH ₂ CH ₃ R ₁₀ = H, C ₁ to C ₄ alkyl

(c) in 0 to 25 mol% with R ₂ to R ₅ = H, C ₁ to C ₈ alkyl radicals

(d) in 0 to 70 mol% with R ₆ , R ₇ = H, C ₁ to C ₈ -alkyl radicals with at least one alkylketene dimer (AKD) of the general formula e)

e) with R ₈ , R _{9 are} each identical or different = C ₈ to C ₃₀ alkyl, C ₈ to C ₁₆ alkyl, C ₁ to C ₂₀ alkyl substituted phenyl, C ₁ to C ₂₀ alkyl substituted cycloalkyl, aralkyl , in organic solvents or in the polymer melt. Method according to one of claims 5 or 6, characterized in that the reaction in a melt, in addition to the polymer with the repeating units a), b), c), d) one or more plasticizers is carried out. Method according to one of claims 5 or 6, characterized in that the reaction in egg An extruder takes place. Use of the reaction products according to one of Claims 1 to 4 for the production of coatings Substrates, as an additive for the production of paper, in particular oil and greaseproof paper and for the production of interlayer films for composite glazing. Use of the reaction products according to one of Claims 1 to 4 as a binder in paints and corrosion inhibitors, as a binder for ceramic green films, ceramic powder and metal powder, as a binder for photographic films or photothermal materials or as binders for printing inks and for the production of interlayer films for composite glazing be used. Foil containing the reaction products of polymers with the repeat units a) to d) with the AKD of the formula e) according to one of claims 1 to 4.